The main ways of removing in carbohydrates. Decarboxylation of aromatic carboxylic acids as reaction of electrophilic substitution Decarboxylation of benzoic acid salts

The reactions of carboxylic acids can be applied to a number of great groups:

1) Updates carboxylic acids

2) Reaction decarboxylation

3) Reactions of substitution at -carbon atom of carboxylic acids

4) Reactions of nucleophilic substitution at the acyl atom in carbon.

We are lastingly visible from the skin of groups of reactions.

18.3.1. Renewal of carboxylic acids

Carboxylic acids and add up to virgin spirits for the additional help of litiyalyumіnіygіdrіda. Renewal of aldehydes and ketones is not required for the renewal of aldehydes and ketones. Carry out renewal when boiling in tetrahydrofuran.

Diborane B 2 H 6 is also an important carboxylic acid to primary alcohols. The renewal of the carboxylic group to CH 2 OH with the help of diborane in THF works in even smaller minds and does not get rid of the functional groups (NO 2; CN;
), Tom tsey method in deyaky vipad appears to be very important.

18.3.2. decarboxylation

Tsim terminom to get along whole group non-mannered reactions, in which CO 2 is added and occur halfway to replace one atom in carbon less, less acidic acid.

In the course of decarboxylation reactions in organic synthesis, in the reaction of Borodin-Hunsdicker, in a mixture of carboxylic acid, when heated with a solution, bromine in CCl 4 is converted into an alkyl halide.

For the successful implementation of the reaction, it is necessary to collect separately dried salts of carboxylic acids and alkyl halide salts to form in wide gaps in the debris from the stage of purification and watery salt. Modification has been added a little, to replace the common vicious mercury salts. Mercury or carboxylic acid is not seen in individual view And in an indifferent distributor, they heat a sum of carboxylic acid, mercury oxide and halogen. The whole method, as a rule, is to produce a high and reproducible output.

For the reaction of Borodin-Hunsdikker, the establishment of a lantsyug radical mechanism. Statements in the first stage of acetylgipobromite undergo homolytic cleavage from the statements of the carboxylic radical and the bromine atom. The carboxylic radical absorbs CO 2 and transforms into an alkyl radical, which then regenerates lancin, splitting off the bromine atom from the acylhydrobromine.

Lantsyuga Ініціюvanня:

Lantsyuga boom:

The original method of oxidative decarboxylation of carboxylic acids by proponation J. Kochi in 1965 rots. Carboxylic acids are oxidized with lead tetraacetate, and when decarboxylation is added to the reaction products, alkanes, alkenes and folding esters of ocetic acids are widely used. The mechanism of the process of reaction has not been established in detail;

Alken and folding ether, mabut, is established from the carbocation as a result of the separation of a proton or the accumulation of acetate-ion. The introduction of the amount of halide-ion into the reaction is practically without any residues causing offense to the processes and to produce alkyl halides to the approval.

Two methods of decarboxylation are good to add one to one. Decarboxylation of Ag or Hg-salts gives the best results for carboxylic acids with the primary radical, while when oxidized with lead tetraacetate in the presence of lithium chloride, the most high-quality alkyl halides are preferable for carboxylic acids from the second.

The most important, however, is the preparative value of the reaction of decarboxylation of carboxylic acids, the electrolytic condensation of salts of carboxylic acids, ascrite in 1849 by G. Kolbe. Win conducting electrolysis of water solution to calcium acetate in the hope of eliminating the CH 3 radical, however, replacing it on the anode by removing ethane. Similarly, in the case of electrolysis of water, the sodium salt of valeric acid is replaced and the butyl radical is replaced by n.octane. Electrochemical oxidation of carboxylate ions has been used historically by the first method to synthesize saturated carbohydrates. With the electrolysis of sodium or calcium salts of boundary aliphatic acids in methanol or aqueous methanol in electrolysis and with platinum electrodes at 0-20 ° C and with a high alkaline stream, the alkane is set up with an output of 50-90%.

However, with the presence of an alkyl group in the-position, it decreases drastically and slightly outweighs 10%.

The reaction was especially cinnamic for the synthesis of dicarboxylic acid derivatives ROOC (CH 2) n COOR s n from 2 to 34 with electrolysis of salts of half-ethers of dicarboxylic acids.

In the current organic electrosynthesis, there is a widespread transcription of electrolytic condensation, such as in the electrolysis of the sum of carboxylic acid salts and the monoester of dicarboxylic acid.

Electrolysis of the range of two salts is produced until the sum is established, three strongly one form of one reaction product is produced, which can be easily broken down by distillation into some components. The whole method allows podovzhuvat in the carbon skeleton of carboxylic acid on whether the number of atoms in carbon is practically in one operation.

Electrolytic condensation is surrounded by salts of carboxylic acids with a non-malignant radical and salts of half-ethers of dicarboxylic acids. The salts of , - і , -unsaturated acids are not susceptible to electrochemical condensation.

For the Kolbe reaction, a radical mechanism is propped up, including three last stages: 1) oxidation of carboxylate ions on the anode to carboxylate radicals
; 2) decarboxylation of cich radicals to alkyl radicals and dioxide in carbon; 3) recombination of alkyl radicals.

With a high degree of concentration of alkaline radicals at the anode during dimerization, with a low degree of strength, alkaline radicals either disproportionate with the approval of an alkene or an alkane or remove an atom of water from the solution.

The salts of carboxylic acids are also decarboxylated during pyrolysis. Coloration of pyrolysis of calcium or barium salts of carboxylic acids is the main method of removing ketones. In the 19th century, "dry distillation" of boolean calcium acetate was the main method for removing acetone.

Nadal was the method of acquiring such a rank that in the new day is the stage of removing the salts. A vapor of carboxylic acid is passed over a catalyst - oxides of manganese, thorium or zirconium at 380-400 0. The most effective and expensive catalyst is oxides of thorium.

In the simplest acid drops, with the number of atoms in carbon, from two to ten, it is converted into symmetric ketones with a flow rate of about 80% when boiling with a powder-like salt at 250-300 . Tsey way to know the stasis in the industry. The most successful pyrolytic method and in the given hour is used for the synthesis of five- and six-membered cyclic ketones from dibasic acids. For example, from the sum of adipic acid and hydroxide bar (5%) at 285-295 , cyclopentanone is recovered with a yield of 75-85%. Cyclooctanone is set up with azelaic acid when heated from ThO 2 with a yield of not more than 20%, this method is not very useful for eliminating cycloalkanones with a large number of atoms in carbon.

In carbohydrates of different classes (alkani, alkeny, alcini, alcadieni, areni) it is possible to remove in different ways.

rejection of alkanes

Cracking alkanes from the ear itself about lshayu lantsyuga

The process, which takes place in the industry, is carried out in the temperature range of 450-500 o C in the presence of the catalyst and at temperatures of 500-700 o C for the duration of the catalyst:

The importance of the industrial process of cracking the field is in the fact that it is necessary to allow the sale of petrol from important fractions of naphtha, but not to become a sutta value by itself.

Gidruvannya of non-saturated carbohydrates

  • alkenes:
  • alkynes and alkadienes:

Gasification of the Kamyaniy Vugilya

in the presence of a nickel catalyst at increased temperatures and a vice can be used to remove methane:

Fischer-Tropsch process

For the help of the given method, there can be some borderline in carbohydrate normal budovi, tobto alkani. Synthesis of alkanes, vikoristyuchi syngas (summy gas CO and water H 2), which is passed through a catalyst at high temperatures and a vice:

Wurtz reaction

For the additional given reaction, you can be rejected in carbohydrates from b about the largest number of atoms in carbon in lantsyuz, lower in vikhid in carbohydrates. Reaction against metal sodium halogenated alkane:

Decarboxylation of carboxylic acid salts

The fusion of solid salts of carboxylic acids in the meadows is carried out to the decarboxylation reaction, at which the carbohydrate is set in a lower number of atoms in the carbon and carbonate metal (Dumas reaction):

Hydrolysis of aluminum carbide

The interaction of aluminum carbide with water, as well as with non-oxidizing acids to produce methane:

Al 4 C 3 + 12H 2 O = 4Al (OH) 3 + 3CH 4

Al 4 C 3 + 12HCl = 4AlCl 3 + 3CH 4

rejection of alkene

cracking alkane

reaction in Zagalom viglyadі in the same bully, a vische is visible (rejection of alkanes). Application of reaction cracking:

dehydrohalogenation of haloalkanes

Dehydrohalogenation of halogenated alkanes against alcohol, when used on them, to a meadow:

alcohol dehydration

The Danish process is processed in the presence of concentrated hydrochloric acid and heated to a temperature of 140 ° C:

Worse respect, in the case of dehydration, and in the case of dehydrohalogenation, the addition of a low molecular weight product (water or hydrogen halide) to follow Zaitsev's rule: water occurs as a hydrogenated atom.

Dehalogenation of vicinal dihaloalkanes

Vіtsіnіm dihalogenoalkanіvіyuyuyuyuyuyut those old in carbohydrates, from which atoms of chlorine are attached to the suspension atoms in the carbon lance.

Dehydrohalogenation of vicinal haloalkanes can be used, zinc or magnesium:

alkane dehydrogenation

Passing alkanes over the catalyst (Ni, Pt, Pd, Al 2 O 3 or Cr 2 O 3) at high temperatures (400-600 o C) to produce the following alkenes:

removal of alkadienes

Dehydrogenation of butane and butene-1

Finding the moment by the main method virobnitstva butadinu-1,3 (divinyl) є catalytic degradation butane, as well as butene-1, can be found in the gases of the secondary refinery of naphtha. The process is carried out in the presence of a catalyst based on chromium (III) oxide at 500-650 ° С:

Due to the high temperatures at the presence of catalysts for isopentane (2-methylbutane), an important industrial product, isoprene, is distilled (a specific word for removing the so-called "natural" rubber):

Lebed's method

Earlier (in the Radiansky Soyuz), butadin-1,3 was trimmed using the Lebedyev method for ethanol:

Dehydrohalogenated dihalogenated alkanes

Zdіysnyuєtsya dієu on halogenated alcoholic beverages in the meadow:

rejecting alkynes

rejecting acetylene

pyrolysis for methane

When heated to a temperature of 1200-1500 ° C, methane undergoes a dehydration reaction with a one-hour tasting of a charcoal lance - acetylene and water are set:

Hydrolysis of carbohydrates in tin and tin earth metals

I wash acetylene in the laboratory using carbide and earth metal and water and non-oxidizing acids. The most cheap і, yak naslіdok, the most affordable for the treatment of calcium carbide:

dehydrohalogenated dihaloalkanes

Removing homologues of acetylene

Dehydrohalogenation of dihaloalkanes:

Dehydrogenation of alkanes and alkenes:

Removing aromatic carbohydrates (areniv)

Decarboxylation of aromatic carboxylic acid salts

By fusion of salts of aromatic carboxylic acids in the meadows, the aromatic in carbohydrates are reduced by a lower number of carbon atoms in the molecule in porous in the organic mixture:

trimerization of acetylene

If acetylene is passed at a temperature of 400 ° C above the assets, benzene will be established with good flow:

In a similar way, it is possible to trim symmetric trialkyl substituted benzene from acetylene homologues. for example:

Dehydrogenation of cyclohexane homologues

When Cycloalkani has 6 atoms in carbon in a cycle of high temperature in the presence of platinum, dehydrogenation occurs with the formulation of a form of aromatic hydrocarbon:

dehydrocyclization

It is also possible to remove aromatic carbohydrates from non-cyclic carbohydrates with the presence of a carbon lancet with 6 or more carbon atoms (dehydrocyclization). The process of running at high temperatures near the presence of platinum or any other catalyst for hydraulic dehydration (Pd, Ni):

Alkylation

Otrimannya homologues to benzene by alkylation of aromatic hydrocarbons in chloroproizovodnimi alkanes, alkenes or alcohols.

Dzherelami of boundary hydrocarbons є naphtha and natural gas. main component natural gas- the simplest methane in the carbohydrate, which is vicorized without the need for an average or to be overrun. Nafta, knitted from the earthly nadr, also bears reprobation, rectification, cracking. The greatest amount of carbohydrates can be removed during the processing of naphtha and іnshih natural resources... Ale is the number of valuable carbohydrates to be consumed piece by piece, synthetic ways.

Isomerization in carbohydrates

The discovery of catalysts for isomerization will accelerate the establishment of carbohydrates with a normalized skeleton from linear carbohydrates. The addition of catalysts allows you to change the temperature cheaply, if there is a reaction.
Isooctane can be used as an additive for the production of gasoline, for the promotion of anti-detonation authorities, and also for the production of gasoline.

Gidruvannya (admission to water) alkenes

As a result of cracking, there is a great number of non-saturated carbohydrates with a subassembly - alkenes. Change of quantity is possible by adding water to the system catalysts for gidruvannya- metal (platinum, paladiy, nickel):

Cracking in the presence of catalysts water cracking... The main products are borderline carbohydrates. In such a rank, p_vischennya vise during cracking ( cracking a viscous vise) Allowing to change the number of gas-like (CH 4 - C 4 H 10) in carbohydrates and to change the amount of 6-10 atoms in carbon instead of heavy carbohydrates in the lancet, which is used to store the basis of gasoline.

Tse buli promislovi ways of eliminating alkanes, which are the basis of industrial processing of the main carbohydrate syruvin - naphtha.

There are now a number of laboratory methods for eliminating alkanes.

Decarboxylation of sodium salts of carboxylic acids

Heating the sodium salt of ocetic acid (sodium acetate) with too much meadow to produce the carboxyl group and methane:

If you substitute sodium acetate with sodium propionate, then ethane, with sodium butanoate - propane, etc.

Würz synthesis

When halogenated alkanes are interconnected with sodium metal, the boundary in carbohydrates and metal halide are formed, for example:

Diya of tin metal for the sum of halogen in carbohydrates (for example, bromethane and bromomethane) is produced before the approval of sums of alkanes (ethane, propane and butane).

!!! Reactions to the synthesis of Würz wede to increase the lanceuga of the boundary carbohydrates.

The reaction, on the basis of the synthesis of Würz, is good against only haloalkanes, in the molecules of which the halogen atom is assigned to the primary atom in carbon.

hydrolysis carbidiv

When processing these carbides, the carbon in the oxidation stage -4 (for example, aluminum carbide), methane is set up with water.

Lecture number 12

CARBONIC ACID

plan

1. The method of rejection.

2. Cheerful authorities.

2.1. Acid power.

2.3. Reactions on a -carbon atom.

2.5. Updates.

2.6. Dicarboxylic acids.


Lecture number 12

CARBONIC ACID

plan

1. The method of rejection.

2. Cheerful authorities.

2.1. Acid power.

2.2. Reactions of nucleophilic substitution.
Functional consumable carboxylic acids.

2.3. Reactions on a -carbon atom.

2.5. Updates.

2.6. Dicarboxylic acids.

1. The method of rejection

2. Chemistry
power

Carboxylic acids and place the carboxyl group, in which without a middle band
itself a carbonyl group і hydroxyl. Їх inwardly injecting
a complex of powers, of the powers of the carboniferous nations and
hydroxyl derivatives. Reactions for the participation of carboxylic acids proceed through
such basic strands.

    1. Substitution of a group UNO pid
      dієyu pіdstav ( acid power).
    2. Interaction with nucleophilic reagents
      by carbonyl atom in carbon ( coverage of functional older and
      renewal)
    3. Reactions on a -carbon atom
      (halogenation)
    4. Decboxylation

2.1. acid
power

Carbonic acids are one of the strongest organic acids. їх water
find a sour reaction.

RCOOH + H 2 O = RCOO - +
H 3 O +

Causes of high acidity of carboxylic acids і
її the presence of nature, defenders in the carbohydrate radical buli
Viewed earlier (div. lek. No. 4).

Carboxylic acids and set up salts at
in conjunction with active metals and more production.

When interacting with strong inorganic
carboxylic acids and can show basic power, attaching
a proton at the carbonyl acid atom.

Protonation of carboxylic acids
for the activation of the carboxylic group in nucleophilic substitution reactions.

For the discovery of the presence of molecules in one hour
acidic and basic centers in carboxylic acids and
Water sounds and sounds in the main in viglyadi dimers (div. lek. №2).

2.2. Reactions of nucleophilic substitution.
Functional consumable carboxylic acids.

The main type of reactions of carboxylic acids is
interaction with nucleophiles with the statements of functional older ones.
Interaction between carboxylic acids and functional
lost, pointed at the schematics.

Presented on diagrams for revenge
acyl group In the course
їх in the unconditional viglyadі go from one day to
іnshe, z'єednuchis with nucleophil. These processes are called acylation,
and carboxylic acids and functional derived - acyl
reagents
... The acylation process can be performed by the inward-looking viewer.
offensive scheme.

In this order, acylation є
the process of nucleophilic substitution of a carbonic atom in carbon.

The mechanism of reaction in the zalny viglyad is clear
occasionally yogo z Ad N -reaction
aldehyde and ketones. Yak and in times of carbonic spoluks, the reaction is to be repaired
s attack of the nucleophil on the carbonyl atom in carbon, which is ineffective
positive charge. When tsomu razriva
p -links in coal-goose and pretend tetrahedral
intermediate
... Wastes of a falsified transformation of an intermediate in carbonyl i
atsilnyh z'єdnan rіznі. Yakshko carbonylny spoluky give a product admitting, Then acyls cleave off the group X and give the product replacement.


The reason for the risky behavior of acyl
carbonic spoluk - in the development of stability of the potential identity of the group X.
In the case of aldehyde and ketone - hydride-anion N — abo carboanion R, Yaki in its high basicity є
supremely filthy to go in groups. U razі acіlnyh z'єdnan X
Significantly larger stable identifier group (Cl
— ,
RCOO -, RO -, NH 2 - ).
NS
for the acid obtained
HX.

Reactivity in terms of delivery before
nucleophiles in carboxylic acids and functional older ones are less, less than
aldehyde and ketones, as well as an effective positive charge on carbonyl
atoms in the carbon are lower for the rakhunok + M-efect of the group X.

The activity of the acyl group is moving in the minds
acid catalysis, since the protonation of the growth is effective
positive charge on the atom in the carbon and fall down on the attack
nucleophilus.

For acylating health
carboxylic acids grow in the first row up to a change
+ M-efect of groupy H.

In a number of rows in front of the anterior segment can be removed from the
by acylation of a generic nucleophil. The process of rejecting bilsh
active acetylating reagents, less active ones are practically not available through
uncomfortable position of the ravnova, for example, is more basic
mina group in some cases with an attacking nucleophilus. all functional
lost can be eliminated without any middle acids and converted into them
with hydrolysis.

Chlorangidridi and anhidridi

methods of rejection

Chlorangydridi will be reconstituted together
carboxylic acids with phosphorus and sulfur halides.

RCOOH + SOCl 2 ® RCOOCl + SO 2 +
HCl

RCOOH + PCl 5 ® RCOOH + POCl 3 +
HCl

Anhydride is established with carboxylic acids
diєyu oxide phosphorus (V).

Zmіshati Angіdridi Mozhut Buti Otrimanі
acylation of salts of carboxylic acids with acid chlorides.



acid chlorides and anhydride.

NS lorangidri and angidridi - the most reactive
carboxylic acids. Їх reactions with nucleophiles occur in soft minds, without
catalyst and practically non-negotiable.

In case of victorious changes of anhydrides from
the nucleophilus will contain an excess of a large weak acid, and anion with a strong
acids and the role of mina group.


V
biochemical reactions of acylation an important role in the development of changes in anhydride
carboxylic acids and phosphoric acid - acetylphosphate and substituted acetylphosphate. Z
the nucleophilus is used to collect an excess of organic acids, and the acetylphosphate-anion
vikonuє role of a good ide group.



folding efiri

methods of rejection

RCOO- Na + + R Cl ® RCOOR + NaCl Using the efficient method of removing folding efirіv є reaction of eterification... Reaction against nucleophilic substitution in
carboxyl group.

Carboxylic acids є weak acyl
reagents through the + M-effect of the OH group. Vikoristannya of the strong
nucleophilic, which at once є і strong bases (for example,
basic catalysis), in this vipad it is unwise, so as the stink of translating carbon
acids in the least reactive salts of carboxylic acids. carry out the reaction
in the sinks of acid catalysis. The role of the acid catalyst is stored as
said, in an increased effective positive charge on the atom in the carbon
carboxyl group, i, in addition, protonation of OH group at the stage
introduction of the transformation in the garnu id group - N 2 O.


All stages of reaction
werewolves. For the change of rvnovagi in the bik process of eterification vikorystovoy
surplus of one of the reagents and the visible products from the spheres of the reaction.

Reactions of nucleophilic substitution in
alkoxycarbonyl group.

Folding efiri - weak acyluyut
reagents, low anhydride and acid chloride. S N -reaction in alkoxycarbonyl group
hard minds and vimagayut acid or basic catalysis. who have chosen
reactions of the type є hydrolysis, aminolysis and
re-verification
.

Hydroliz.

Folding ethers are hydrolyzed with the approval of carboxylic acids before
acids abo lugiv.

Acid hydrolysis of folding ethers is the whole reaction of ringing energy.

Mechanism of acid hydrolysis, including those stages,
and the process of eterification, albeit in the ecstatic aftermath.

Luzhniy gidroliz of folding efirіv vimagau
Equivalent amounts to the meadow and non-negotiable.

RCOOR + NaOH ® RCOO - Na + + R OH

The essence of luzhny katalizu polyagaє in vikoristannі
replacement of a weak nucleophil - lead, more strong nucleophil -
hydroxide-ion.


invisibility to the process
to get a low response rate to nucleophilia
to the hydrolysis product - carboxylate anion.

Retrieval.

The role of the nucleophile in the reaction
viconu is an alcohol molecule. The process is catalyzed by acids abo
pіdstavami.


Mechanism of reaction is analogous to that of folding
efiriv. Reinterference is a turnaround process. For zsuvu rivnovagi to the right
a great surplus of alcoholic alcohol is necessary. reaction
redefinition of storage for rejection of folding fatty acid esters
s triacylglicerides (div. lek. 18)

Aminolizu.

Folding ether acyl ammonium and amino acid
about the amidiv of carboxylic acids.

Amidi carboxylic acids

Budova amide group

A My group is to learn from the bagatokh biologically important events,
First for everything in peptides and proteins (peptide link). Її electronic
spaciousness of budova is rich in chomu viznachaє їх biologic
function.

Amidna group is a p-p -conjugated system, in which it is displayed
additionally recirculating the p-orbital of the atom to nitrogen s
p -orbitaly link
in coal-goose.

Such a rozpodil electronic power
to produce an energetic bar'єru wrapping around link C-N up to 60 -
90 kJ / mol. As a result, the amide compound is less flat than Budova, and the result is
C-N і С = O may seem to be less or more than theirs
quantities.

The visibility of the wrap is about call C-N
to bring to the point of amidivs cis-і trance-isomers. for
more amidiv in short є trance-configuratsii.

The peptide link is also maє trance-configuration, in which basic radicals of amino acid surpluses
most visible one from one

methods of rejection

Reactions of nucleophilic substitution in
carboxamide group.

Amid is the best reaction-grade waste carboxylic acids. For them
from reactions to hydrolysis, which are going on in hard minds before
water solutions of acids abo luv.

Mechanisms of reactions of analogous hydrolysis of folding
efiriv. However, on the basis of hydrolysis of efіrіv, acidic and hydrolysis hydrolysis
amidiv pass through neatly.

2.3. Reactions on a -carbon
atom

Carboxylic acids a -hydrogen atoms,
interchange with bromine in the presence of phosphorus with approval
a - bromine derivatives
(reaction of Hell - Forgald - Zelinsky
)

Halogen in a -halogenated acids are easily replaced by
for a number of nucleophilic reagents. Tom
a -halogenated acids
є edgy words in the synthesis of a wide range of substitutes for
a -stead
acids, including
a-amino- i a -hydroxy acid.

2.4.
decarboxylation

Decarboxylation - the goal of CO 2 elimination from carboxylic acids and salts. decarboxylation
carry out the heating path in the presence of acids or before. When tsomu, yak
as a rule, the substitution of a carboxylic group for an atom is considered.

Independent monocarboxylic acids
decarboxylated in hard minds.

Decarboxylation to lodge when exposed
electronically accepted intercessors in a-put.

The more important value is enzymatic
decarboxylation of keto, amino and hydroxy acids in organisms (div. lek. No. 14 that
16).

Decarboxylation by means of a heating bar (dry
distillation) of calcium and baric salts of carboxylic acids - the method of removing
ketones.

2.5.
Updates.

Carboxylic acids, chlorohydrides, anhydrides and folding ethers
updated by LiAlH 4 to the first
alcohol.

Chlorahydride can be updated to
aldegidiv (div. lek. No. 11).

When renewing amide of carboxylic acids
amіni.

3. Dicarboxylic acids

Dicarboxylic acids and two carboxyl groups. most accessible
є Acid lineage, which can be removed from 2 to 6 atoms in carbon. їх
Budov and the methods of rejection are presented in Table 9. bacteria

Chemical power of dicarboxylic acids in
the main analogue power of monocarboxylic acids. Stinks give all the reactions,
characteristic for the carboxyl group. If you can, you will be rejected
functional erasure (chloroanhydride, anhydride, folding, efiri, amidi) yak
for one, so and for offense carboxyl
groups. Dicarboxylic acids and may have a high acidity, less monocarboxylic,
inherited from the I-effect of the carboxylic group. In the world of zbіlshennya vіdstanі mіzh
by carboxyl groups, the acidity of dicarboxylic acids changes (div. table.
9).

In addition, dicarboxylic acids and a number of
specific powers that appear in molecules of two
carboxyl groups.

Dicarboxylic acid stirring up to
loading.

Reconstitution of dicarboxylic acids during heating
lie down in the form of a lantsyuga dozhini, which will produce carboxyl groups, and start
the possibility of establishing thermodynamically stable five- and six-membered
cycle.

When heating oxalic and malonic acids
decarboxylation.

Amber, glutaric and maleic acids at
Heated it is easy to draw water from the statements of five-and six-membered cyclic
angidridiv.

Adipic acid when heated
it is decarboxylated from the statements of the cyclic ketone - cyclopentanone.

polycondensation reactions

D carboxylic acids and interaction with diamini and diola with
about polyamides and polyphics, which can be found in
virobnistvі synthetic fibers.

Biologically important dicarbons
acid.

Oxalic acid I will approve important salts, for example,
calcium oxalate, which is deposited at the viglyadi stones in the nirkah and in the chaff.

Burshtinic acid take part in the exchange processes that go through
organism. Chi є for industrial processes in tricarboxylic acid cycle.

Fumaric acid, on vidminu vid maleinova , widely expanded in nature, take care of the fate in the process
exchange of rechovin, seed cream in cyclic tricarboxylic acids.

Lecture number 12

CARBONIC ACID

plan

1. The method of rejection.

2. Cheerful authorities.

2.1. Acid power.

2.3. Reactions on a -carbon atom.

2.5. Updates.

2.6. Dicarboxylic acids.


Lecture number 12

CARBONIC ACID

plan

1. The method of rejection.

2. Cheerful authorities.

2.1. Acid power.

2.2. Reactions of nucleophilic substitution.
Functional consumable carboxylic acids.

2.3. Reactions on a -carbon atom.

2.5. Updates.

2.6. Dicarboxylic acids.

1. The method of rejection

2. Chemistry
power

Carboxylic acids and place the carboxyl group, in which without a middle band
itself a carbonyl group і hydroxyl. Їх inwardly injecting
a complex of powers, of the powers of the carboniferous nations and
hydroxyl derivatives. Reactions for the participation of carboxylic acids proceed through
such basic strands.

    1. Substitution of a group UNO pid
      dієyu pіdstav ( acid power).
    2. Interaction with nucleophilic reagents
      by carbonyl atom in carbon ( coverage of functional older and
      renewal)
    3. Reactions on a -carbon atom
      (halogenation)
    4. Decboxylation

2.1. acid
power

Carbonic acids are one of the strongest organic acids. їх water
find a sour reaction.

RCOOH + H 2 O = RCOO - +
H 3 O +

Causes of high acidity of carboxylic acids і
її the presence of nature, defenders in the carbohydrate radical buli
Viewed earlier (div. lek. No. 4).

Carboxylic acids and set up salts at
in conjunction with active metals and more production.

When interacting with strong inorganic
carboxylic acids and can show basic power, attaching
a proton at the carbonyl acid atom.

Protonation of carboxylic acids
for the activation of the carboxylic group in nucleophilic substitution reactions.

For the discovery of the presence of molecules in one hour
acidic and basic centers in carboxylic acids and
Water sounds and sounds in the main in viglyadi dimers (div. lek. №2).

2.2. Reactions of nucleophilic substitution.
Functional consumable carboxylic acids.

The main type of reactions of carboxylic acids is
interaction with nucleophiles with the statements of functional older ones.
Interaction between carboxylic acids and functional
lost, pointed at the schematics.

Presented on diagrams for revenge
acyl group In the course
їх in the unconditional viglyadі go from one day to
іnshe, z'єednuchis with nucleophil. These processes are called acylation,
and carboxylic acids and functional derived - acyl
reagents
... The acylation process can be performed by the inward-looking viewer.
offensive scheme.

In this order, acylation є
the process of nucleophilic substitution of a carbonic atom in carbon.

The mechanism of reaction in the zalny viglyad is clear
occasionally yogo z Ad N -reaction
aldehyde and ketones. Yak and in times of carbonic spoluks, the reaction is to be repaired
s attack of the nucleophil on the carbonyl atom in carbon, which is ineffective
positive charge. When tsomu razriva
p -links in coal-goose and pretend tetrahedral
intermediate
... Wastes of a falsified transformation of an intermediate in carbonyl i
atsilnyh z'єdnan rіznі. Yakshko carbonylny spoluky give a product admitting, Then acyls cleave off the group X and give the product replacement.


The reason for the risky behavior of acyl
carbonic spoluk - in the development of stability of the potential identity of the group X.
In the case of aldehyde and ketone - hydride-anion N — abo carboanion R, Yaki in its high basicity є
supremely filthy to go in groups. U razі acіlnyh z'єdnan X
Significantly larger stable identifier group (Cl
— ,
RCOO -, RO -, NH 2 - ).
NS
for the acid obtained
HX.

Reactivity in terms of delivery before
nucleophiles in carboxylic acids and functional older ones are less, less than
aldehyde and ketones, as well as an effective positive charge on carbonyl
atoms in the carbon are lower for the rakhunok + M-efect of the group X.

The activity of the acyl group is moving in the minds
acid catalysis, since the protonation of the growth is effective
positive charge on the atom in the carbon and fall down on the attack
nucleophilus.

For acylating health
carboxylic acids grow in the first row up to a change
+ M-efect of groupy H.

In a number of rows in front of the anterior segment can be removed from the
by acylation of a generic nucleophil. The process of rejecting bilsh
active acetylating reagents, less active ones are practically not available through
uncomfortable position of the ravnova, for example, is more basic
mina group in some cases with an attacking nucleophilus. all functional
lost can be eliminated without any middle acids and converted into them
with hydrolysis.

Chlorangidridi and anhidridi

methods of rejection

Chlorangydridi will be reconstituted together
carboxylic acids with phosphorus and sulfur halides.

RCOOH + SOCl 2 ® RCOOCl + SO 2 +
HCl

RCOOH + PCl 5 ® RCOOH + POCl 3 +
HCl

Anhydride is established with carboxylic acids
diєyu oxide phosphorus (V).

Zmіshati Angіdridi Mozhut Buti Otrimanі
acylation of salts of carboxylic acids with acid chlorides.



acid chlorides and anhydride.

NS lorangidri and angidridi - the most reactive
carboxylic acids. Їх reactions with nucleophiles occur in soft minds, without
catalyst and practically non-negotiable.

In case of victorious changes of anhydrides from
the nucleophilus will contain an excess of a large weak acid, and anion with a strong
acids and the role of mina group.


V
biochemical reactions of acylation an important role in the development of changes in anhydride
carboxylic acids and phosphoric acid - acetylphosphate and substituted acetylphosphate. Z
the nucleophilus is used to collect an excess of organic acids, and the acetylphosphate-anion
vikonuє role of a good ide group.



folding efiri

methods of rejection

RCOO- Na + + R Cl ® RCOOR + NaCl Using the efficient method of removing folding efirіv є reaction of eterification... Reaction against nucleophilic substitution in
carboxyl group.

Carboxylic acids є weak acyl
reagents through the + M-effect of the OH group. Vikoristannya of the strong
nucleophilic, which at once є і strong bases (for example,
basic catalysis), in this vipad it is unwise, so as the stink of translating carbon
acids in the least reactive salts of carboxylic acids. carry out the reaction
in the sinks of acid catalysis. The role of the acid catalyst is stored as
said, in an increased effective positive charge on the atom in the carbon
carboxyl group, i, in addition, protonation of OH group at the stage
introduction of the transformation in the garnu id group - N 2 O.


All stages of reaction
werewolves. For the change of rvnovagi in the bik process of eterification vikorystovoy
surplus of one of the reagents and the visible products from the spheres of the reaction.

Reactions of nucleophilic substitution in
alkoxycarbonyl group.

Folding efiri - weak acyluyut
reagents, low anhydride and acid chloride. S N -reaction in alkoxycarbonyl group
hard minds and vimagayut acid or basic catalysis. who have chosen
reactions of the type є hydrolysis, aminolysis and
re-verification
.

Hydroliz.

Folding ethers are hydrolyzed with the approval of carboxylic acids before
acids abo lugiv.

Acid hydrolysis of folding ethers is the whole reaction of ringing energy.

Mechanism of acid hydrolysis, including those stages,
and the process of eterification, albeit in the ecstatic aftermath.

Luzhniy gidroliz of folding efirіv vimagau
Equivalent amounts to the meadow and non-negotiable.

RCOOR + NaOH ® RCOO - Na + + R OH

The essence of luzhny katalizu polyagaє in vikoristannі
replacement of a weak nucleophil - lead, more strong nucleophil -
hydroxide-ion.


invisibility to the process
to get a low response rate to nucleophilia
to the hydrolysis product - carboxylate anion.

Retrieval.

The role of the nucleophile in the reaction
viconu is an alcohol molecule. The process is catalyzed by acids abo
pіdstavami.


Mechanism of reaction is analogous to that of folding
efiriv. Reinterference is a turnaround process. For zsuvu rivnovagi to the right
a great surplus of alcoholic alcohol is necessary. reaction
redefinition of storage for rejection of folding fatty acid esters
s triacylglicerides (div. lek. 18)

Aminolizu.

Folding ether acyl ammonium and amino acid
about the amidiv of carboxylic acids.

Amidi carboxylic acids

Budova amide group

A My group is to learn from the bagatokh biologically important events,
First for everything in peptides and proteins (peptide link). Її electronic
spaciousness of budova is rich in chomu viznachaє їх biologic
function.

Amidna group is a p-p -conjugated system, in which it is displayed
additionally recirculating the p-orbital of the atom to nitrogen s
p -orbitaly link
in coal-goose.

Such a rozpodil electronic power
to produce up to an energetic bar'єru wrapping around the ring C-N up to 60 -
90 kJ / mol. As a result, the amide compound is less flat than Budova, and the result is
C-N і С = O may seem to be less or more than theirs
quantities.

Visibility of the wrap around the sound C-N
to bring to the point of amidivs cis-і trance-isomers. for
more amidiv in short є trance-configuratsii.

The peptide link is also maє trance-configuration, in which basic radicals of amino acid surpluses
most visible one from one

methods of rejection

Reactions of nucleophilic substitution in
carboxamide group.

Amid is the best reaction-grade waste carboxylic acids. For them
from reactions to hydrolysis, which are going on in hard minds before
water solutions of acids abo luv.

Mechanisms of reactions of analogous hydrolysis of folding
efiriv. However, on the basis of hydrolysis of efіrіv, acidic and hydrolysis hydrolysis
amidiv pass through neatly.

2.3. Reactions on a -carbon
atom

Carboxylic acids a -hydrogen atoms,
interchange with bromine in the presence of phosphorus with approval
a - bromine derivatives
(reaction of Hell - Forgald - Zelinsky
)

Halogen in a -halogenated acids are easily replaced by
for a number of nucleophilic reagents. Tom
a -halogenated acids
є edgy words in the synthesis of a wide range of substitutes for
a -stead
acids, including
a-amino- i a -hydroxy acid.

2.4.
decarboxylation

Decarboxylation - the goal of CO 2 elimination from carboxylic acids and salts. decarboxylation
carry out the heating path in the presence of acids or before. When tsomu, yak
as a rule, the substitution of a carboxylic group for an atom is considered.

Independent monocarboxylic acids
decarboxylated in hard minds.

Decarboxylation to lodge when exposed
electronically accepted intercessors in a-put.

The more important value is enzymatic
decarboxylation of keto, amino and hydroxy acids in organisms (div. lek. No. 14 that
16).

Decarboxylation by means of a heating bar (dry
distillation) of calcium and baric salts of carboxylic acids - the method of removing
ketones.

2.5.
Updates.

Carboxylic acids, chlorohydrides, anhydrides and folding ethers
updated by LiAlH 4 to the first
alcohol.

Chlorahydride can be updated to
aldegidiv (div. lek. No. 11).

When renewing amide of carboxylic acids
amіni.

3. Dicarboxylic acids

Dicarboxylic acids and two carboxyl groups. most accessible
є Acid lineage, which can be removed from 2 to 6 atoms in carbon. їх
Budov and the methods of rejection are presented in Table 9. bacteria

Chemical power of dicarboxylic acids in
the main analogue power of monocarboxylic acids. Stinks give all the reactions,
characteristic for the carboxyl group. If you can, you will be rejected
functional erasure (chloroanhydride, anhydride, folding, efiri, amidi) yak
for one, so and for offense carboxyl
groups. Dicarboxylic acids and may have a high acidity, less monocarboxylic,
inherited from the I-effect of the carboxylic group. In the world of zbіlshennya vіdstanі mіzh
by carboxyl groups, the acidity of dicarboxylic acids changes (div. table.
9).

In addition, dicarboxylic acids and a number of
specific powers that appear in molecules of two
carboxyl groups.

Dicarboxylic acid stirring up to
loading.

Reconstitution of dicarboxylic acids during heating
lie down in the form of a lantsyuga dozhini, which will produce carboxyl groups, and start
the possibility of establishing thermodynamically stable five- and six-membered
cycle.

When heating oxalic and malonic acids
decarboxylation.

Amber, glutaric and maleic acids at
Heated it is easy to draw water from the statements of five-and six-membered cyclic
angidridiv.

Adipic acid when heated
it is decarboxylated from the statements of the cyclic ketone - cyclopentanone.

polycondensation reactions

D carboxylic acids and interaction with diamini and diola with
about polyamides and polyphics, which can be found in
virobnistvі synthetic fibers.

Biologically important dicarbons
acid.

Oxalic acid I will approve important salts, for example,
calcium oxalate, which is deposited at the viglyadi stones in the nirkah and in the chaff.

Burshtinic acid take part in the exchange processes that go through
organism. Chi є for industrial processes in tricarboxylic acid cycle.

Fumaric acid, on vidminu vid maleinova , widely expanded in nature, take care of the fate in the process
exchange of rechovin, seed cream in cyclic tricarboxylic acids.